Water dispersible, hydroxyl-terminated, fluorinated polyurethanes and method of preparing the same

ABSTRACT

Fluorinated polyurethanes and methods of making the same are provided. The fluorinated polyurethanes are useful for making polyurethane coating compositions for use in aerospace and other applications. The method includes a “split process” by which a hydroxypolyalkylenoxy derivative of a perfluoropolyoxyalkane is separately reacted with isocyanate to produce an isocyanate-terminated compound. The isocyanate-terminated compound is then reacted with an emulsifier to produce an acid- and hydroxyl-functional compound. The acid- and hydroxyl-functional compound is then reacted with isocyanate to form an acid-functional, isocyanate-terminated compound. The acid-functional, isocyanate-terminated compound is then reacted with at least one polyol to produce a higher molecular weight, acid- and hydroxyl-functional compound. Finally, the acid functional groups of the high molecular weight, acid- and hydroxyl-functional compound are neutralized to form a fluoro-urethane salt which is dispersed in water. The resulting fluorinated polyurethane can be used to prepare a polyurethane coating composition.

CROSS-REFERENCE TO RELATED APPLICATION(S)

This application claims priority to and the benefit of U.S. ProvisionalApplication Ser. No. 60/992,835, filed Dec. 6, 2007 and titled, “WATERDISPERSIBLE HYDROXYL-TERMINATED FLUORO-URETHANE COMPOUNDS AND METHOD OFPREPARING THE SAME,” the entire content of which is incorporated hereinby reference.

FIELD OF THE INVENTION

The invention is directed to water dispersible fluorinated polyurethanesuseful in the preparation of coatings for use in aerospace and otherapplications. In addition, the invention is directed to methods ofpreparing the fluorinated polyurethanes.

BACKGROUND OF THE INVENTION

Recently, water-borne polyurethane coating compositions have beendeveloped in an effort to reduce atmospheric pollution caused by organicsolvents, including volatile organic compounds (“VOC”s) and hazardousair pollutants (“HAP”s), which have come under strict environmentalregulations. In addition to reducing VOCs and HAPs in the coatingcompositions, efforts have been made to optimize the performancecharacteristics of water-borne polyurethane coatings. To that end,attempts have been made to use fluorinated diols and polyols in thepreparation of pre-polymers for mixture with isocyanate to yieldfluorinated polyurethane coating compositions. The fluorine atoms in theresulting coating compositions have unique rotation patterns that serveto prevent penetration of foreign substances to the carbon backbones ofthe polymers, making it easy to keep the coatings looking clean. Forexample, because the fluorine atoms prevent foreign substances fromaccessing the carbon backbone, substances such as graffiti may be easilywashed away with water.

Given the desirability of fluorinated coating compositions and the needto reduce VOCs and HAPs, efforts have been made to prepare fluorinatedwater-borne polyurethane coating compositions. Anionic polyurethanedispersions, for example, are typically prepared by first synthesizingan isocyanate-terminated pre-polymer. This process yields anisocyanate-terminated pre-polymer which can be neutralized with tertiaryamines followed by dispersion in water and chain extension, yielding ahigh molecular weight polyurethane dispersion. However, the batchprocess yields a polyol dispersion having poor stability and produces avery low yield of the desired fluorinated pre-polymer. This is becausethe isocyanate reacts not only with the fluorinated diol, but also withthe polyether or polyester polyol and the emulsifier. In fact, theisocyanate does not react well with the fluorinated diol or polyol atall, but instead reacts with the emulsifier and the polyether orpolyester polyol, due to the hydrophobicity of the fluorinated diol orpolyol. The lack of reaction between the fluorinated diol or polyol andthe isocyanate causes the fluorinated diol to phase separate out of thepolyurethane dispersion over time. Indeed, the fluorinated dioltypically separates from the dispersion overnight.

In addition to low yield of the intended high molecular weightfluorinated pre-polymer and the low reactivity (or rate of reaction) ofthe isocyanate with the fluorinated diol or polyols, the batch processprepares polymers (or species) with unpredictable chemical structures.Because the isocyanate reacts with OH groups randomly, and because thefluorinated diols or polyols, the internal emulsifier, and the polyetheror polyester polyols all have multiple OH functionality, it is verydifficult to predict with which OH groups the isocyanate will react andin which order. Therefore, the batch process produces an unlimitednumber of reaction products with different statistical distributions ofthe reactants. Achieving greater control in polymer synthesis would bedesirable.

SUMMARY OF THE INVENTION

The invention is directed to fluorinated polyurethanes and methods ofmaking the same. In addition, the invention is directed to thepolyurethane coating compositions including the fluorinatedpolyurethanes.

According to one aspect of the invention, a method of preparing afluorinated polyurethane includes a “split process” by which ahydroxypolyalkylenoxy derivative of a perfluoropolyoxyalkane is reactedwith a first isocyanate to produce an isocyanate-terminated compound.The isocyanate-terminated compound is then reacted with an emulsifier toproduce an acid- and hydroxyl-functional compound. The acid- andhydroxyl-functional compound is then reacted with a second isocyanate toform an acid-functional, isocyanate-terminated compound. Theacid-functional, isocyanate-terminated compound is then reacted with atleast one polyol to produce an OH-terminated, high molecular weight,acid- and hydroxyl-functional compound. Finally, the acid functionalgroups of the high molecular weight, acid- and hydroxyl-functionalcompound are neutralized to form a fluoro-urethane salt which isdispersed in water. The inventive fluorinated polyurethanes are used toprepare polyurethane coating compositions.

In one embodiment of the invention, the hydroxypolyalkylenoxy derivativeof a perfluoropolyoxyalkane has the formula (1), where theperfluoropolyoxyalkyl group X has the formula (1A); and is reacted witha first isocyanate to form an isocyanate-terminated compound having theformula (2). In one exemplary embodiment, the first isocyanate is adiisocyanate represented by OCN—R—NCO, in which R is selected fromaliphatic groups, cycloaliphatic groups, aromatic groups, and mixturesthereof. Mixtures of isocyanates may also be used. However, using amixture of isocyanates will lessen the predictability of the resultingchemical structure.

HO(H₂CH₂CO)_(n)H₂C—X—CH₂(OCH₂CH₂)_(n)OH  (1)

—CF₂O(CF₂CF₂O)_(p)(CF₂O)_(q)CF₂—  (1A)

OCN—R—(H₂CH₂CO)_(n)H₂C—X—CH₂(OCH₂CH₂)_(n)—R—NCO  (2)

The isocyanate-terminated compound (2) is reacted with an emulsifierrepresented by the formula (3A) to form an acid- and hydroxyl-functionalcompound represented by the formula (4). The emulsifier is representedby Formula 3A, in which R₁ is an alkyl group.

The acid- and hydroxyl-functional compound (4) is reacted with a secondisocyanate to form an acid-functional, isocyanate-terminated compoundrepresented by the formula (5). In one embodiment, the second isocyanateis a diisocyanate represented by OCN—R₂—NCO, in which R₂ is selectedfrom aromatic groups, aliphatic groups, cycloaliphatic groups, andmixtures thereof. Mixtures of isocyanates may also be used. However,using a mixture of isocyanates will lessen the predictability of theresulting chemical structure.

The acid-functional, isocyanate-terminated compound (5) is then reactedwith at least one polyol to form a high molecular weight, acid- andhydroxyl-functional polyurethane compound represented by the formula(6). In one embodiment, the polyol is represented by HO—R₃—OH, where R₃is a polyether group, polyester group, acrylic group, or polyurethanegroup. Mixtures of polyols may also be used. However, using a mixture ofpolyols will lessen the predictability of the resulting chemicalstructure.

Finally, the high molecular weight, acid- and hydroxyl-functionalpolyurethane compound (6) is neutralized with a tertiary amine to form afluorinated polyurethane represented by the formula (7). The tertiaryamine is represented by NR′₃.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is directed to water dispersible fluorinatedpolyurethanes and to methods of preparing the same. The waterdispersible fluorinated polyurethanes are useful as base components influorinated polyurethane coating compositions. The resulting coatingcompositions are useful for aerospace and other applications.

In one embodiment, a water-dispersible fluorinated polyurethane isprepared by a “split process” involving first reacting ahydroxypolyalkylenoxy derivative of a perfluoropolyoxyalkane withisocyanate. The term “split process” refers to the separate reactionsteps in the inventive methods. While the conventional batch processinvolves reacting all reactants simultaneously, the split process of thepresent invention reacts the reactants in a step-wise fashion.

The split process involves first reacting a hydroxypolyalkylenoxyderivative of a perfluoropolyoxyalkane with a first isocyanate toproduce an isocyanate-terminated compound. The isocyanate-terminatedcompound is then reacted with an emulsifier to produce an acid- andhydroxyl-functional compound. The acid- and hydroxyl-functional compoundis then reacted with a second isocyanate to form an acid-functional,isocyanate-terminated compound. The acid-functional,isocyanate-terminated compound is then reacted with at least one polyolto produce a high molecular weight, acid- and hydroxyl-functionalcompound. Finally, the acid functional groups of the high molecularweight, acid- and hydroxyl-functional compound are neutralized to form afluoro-urethane salt compound which is dispersed in water. The inventivefluorinated polyurethanes may be used to prepare polyurethane coatingcompositions.

According to one embodiment, the hydroxypolyalkylenoxy derivative of theperfluoropolyoxyalkane starting material is a hydroxypolyethylenoxyderivative of a perfluoropolyoxyalkane and may be represented by theformula (1).

HO(H₂CH₂CO)_(n)H₂C—X—CH₂(OCH₂CH₂)_(n)OH  (1)

In Formula 1, n is any rational number, for example from 1 to 10, and Xis represented by the formula 1A. In one embodiment, for example, nranges from 1 to 5. In another embodiment, n ranges from 1 to 3

—CF₂O(CF₂CF₂O)_(p)(CF₂O)_(q)CF₂—  (1A)

In Formula 2, p and q are rational numbers, the sum of which (p+q)ranges from 10 to 180. In addition, the ratio of p/q ranges from 0.5 to2. Nonlimiting examples of suitable starting materials satisfyingformulae 1 and 1A include polymer modifiers such as Fluorolink E,Fluorolink E10 and Fluorolink E10-H commercially available from SolvaySolexis, Inc.

Despite the hydrophilic end groups of the starting material representedby formulae 1 and 1A, the starting compound is extremely hydrophobic andhas a relatively low molecular weight. These properties make thecompound represented by formulae 1 and 1A a bad candidate forcombination with water-dispersible isocyanate to form a polyurethanecoating composition. Accordingly, one method of the present inventionincludes first reacting the starting material represented by formula 1with a first isocyanate. In one embodiment, the first isocyanatereactant is a diisocyanate represented by OCN—R—NCO, in which R may beselected from any suitable aromatic groups, aliphatic groups,cycloaliphatic groups, and mixtures thereof. However, any isocyanateknown and used in the polyurethane coating composition field may be usedas the first isocyanate in this reaction. Although diisocyanate may beused, isocyanates of higher functionality are also suitable. Nonlimitingexamples of suitable isocyanates for the first isocyanate includeisophorone diisocyanate, cycloaliphatic diisocyanates (such as thosecommercially available under the trade name Desmodur-W from BayerMaterial Science), hexamethylene diisocyanate (HDI) andtetramethylxylylene diisocyanate (TMXDI). More nonlimiting examples ofsuitable isocyanates are disclosed in U.S. Pat. No. 4,913,972, theentire content of which is incorporated herein by reference. Mixtures ofisocyanates may also be used. However, using a mixture of isocyanateswill lessen the predictability of the resulting chemical structure. Theresulting product is an isocyanate-terminated compound represented bythe formula (2).

OCN—R—(H₂CH₂CO)_(n)H₂C—X—CH₂(OCH₂CH₂)_(n)—R—NCO  (2)

In Formula 2, n and X are the same as in Formula 1.

After reacting the hydroxypolyalkylenoxy derivative of aperfluoropolyoxyalkane (1) with a first isocyanate to produce theisocyanate-terminated compound (2), the isocyanate-terminated compound(2) is reacted with an emulsifier to produce an acid- andhydroxyl-functional compound. The emulsifier is selected from dialkylolpropionic acids which are represented by the formula (3A).

In the emulsifier (3A), R₁ may be any alkyl group. In one embodiment, R₁is selected from methyl groups (as shown in the formula (3B) below) andethyl groups (as shown in the formula (3C) below). Accordingly,nonlimiting examples of suitable emulsifiers for use in this reactioninclude dimethylolbutyric acid (in which R₁ is a methyl group) anddiethylolpropionic acid (in which R₁ is an ethyl group). Mixtures ofemulsifiers may also be used. However, using a mixture of emulsifierswill lessen the predictability of the resulting chemical structure.

The isocyanate groups (NCO groups) of the isocyanate-terminate compound(2) are highly reactive and would normally react with both the hydroxyland carboxyl groups of an emulsifier. However, in the present invention,reaction with the carboxyl group of the emulsifier is stericallyhindered by the presence of an alkyl group (i.e., CH₃ in formula (3B),and C₂H₅ in formula (3C)). Accordingly, the isocyanate groups of theisocyanate-terminated compound (2) selectively react with the hydroxylend groups of the emulsifier (3A) to produce a compound terminated withemulsifier moieties which have both acid and hydroxyl functionalities.The resulting compound is an acid- and hydroxyl-functional compoundrepresented by the formula (4).

In the acid- and hydroxyl-functional compound (4), X and n are the sameas in the hydroxypolyalkylenoxy derivative of a perfluoropolyoxyalkane(1), and R and R₁ are as described above with respect to the isocyanatereactant and the emulsifier (3A).

While the reaction of the isocyanate-terminated compound (2) with theemulsifier (3A) provides acid and hydroxyl functionality, the resultingacid- and hydroxyl-functional compound (4) has low molecular weight andis desirably further reacted to build molecular weight. To further reactthe acid- and hydroxyl-functional compound (4), the method furthercomprises replacing the hydroxyl end groups with isocyanate end groupsto increase reactivity. Accordingly, the acid- and hydroxyl-functionalcompound (4) is reacted with a second isocyanate (which may be the sameas or different from the first isocyanate) to produce anisocyanate-terminated compound represented by the formula (5).

In one embodiment, the second isocyanate reactant is a diisocyanaterepresented by OCN—R₂—NCO, in which R₂ (like R in the first isocyanatereactant, described above) may be selected from any suitable aromaticgroups, aliphatic groups, cycloaliphatic groups, and mixtures thereof.However, any isocyanate known and used in polyurethane coatingcompositions may be used as the second isocyanate in this reaction.Although diisocyanates may be used, multifunctional isocyanates are alsosuitable. Nonlimiting examples of suitable isocyanates for the secondisocyanate include those mentioned earlier with respect to the firstisocyanate.

The isocyanate-terminated compound (5) is then reacted with one or morepolyols to build molecular weight and terminate the compound withhydroxyl groups. The polyol may be any suitable polyol known and used inpolyurethane coating compositions. In one embodiment, the polyol may berepresented by HO—R₃—OH, in which R₃ may be any polyether group,polyester group, acrylic group or polyurethane group. That is, thepolyol may be any polyether polyol, polyester polyol, polyurethanepolyol, or acrylic polyol. Nonlimiting examples of suitable polyolsinclude the organic polyols discussed in U.S. Pat. No. 4,913,972, theentire content of which is incorporated herein by reference. Mixtures ofpolyols may also be used. However, using a mixture of polyols willlessen the predictability of the resulting chemical structure. Thehydroxyl-terminated product resulting from this reaction is representedby formula (6).

In the hydroxyl-terminated compound (6), n, R, R₁ and R₂ are asdescribed above with respect to the hydroxypolyalkylenoxy derivative ofa perfluoropolyoxyalkane (1), the first and second isocyanate reactantsand the emulsifier (3A).

The hydroxyl-terminated compound (6) is then reacted with a tertiaryamine to neutralize at least some of the carboxyl groups present incompound (6). The tertiary amine is represented by NR′₃. One nonlimitingexample of a suitable tertiary amine is triethyl amine. Reaction of thehydroxyl-terminated compound (6) with the tertiary amine yields afluoro-urethane salt represented by formula (7).

Once the hydroxyl-terminated compound is neutralized to form thefluoro-urethane salt (7), the salt is dispersed in water. When dispersedin water, the compound forms micelles in the water. The water-dispersedfluoro-urethane salt compound may then be reacted with water-dispersibleisocyanate to form a polyurethane coating composition for application toa substrate.

Alternatively, if higher molecular weight is desired, prior todispersion in water, the fluoro-urethane salt compound (7) may befurther chain-extended with additional diisocyanates to achieve highermolecular weight. When the desired molecular weight is achieved, theisocyanate-terminated compound may then be reacted with additionalpolyols to yield a hydroxyl-terminated compound, which is then dispersedin water.

Unlike in conventional coating compositions prepared using the batchprocess, the inventive fluoro-compounds are stable when stored in water.The fluoro-compounds remain dispersed and do not phase separate afterdispersion in water. In contrast, in conventional coating compositionsmade from fluorinated diols subjected to the batch process, thefluorinated diol phase separates shortly after dispersion in water.Accordingly, unlike conventional coating compositions, thefluoro-compounds of the present invention retain the benefits impartedby the fluorine atoms protecting the carbon backbone of the polymer.

In addition to retaining the benefits imparted by the fluorine atoms,the fluorinated polyurethanes of the present invention have controllablechemical structures. The conventional batch process of preparing highmolecular weight fluorinated pre-polymers for use in coatingcompositions yields an unlimited number of possible chemical structuresfor the resulting pre-polymer. In the batch process, allhydroxyl-containing reactants are reacted simultaneously with theisocyanate, providing the isocyanate groups numerous OH groups withwhich to react, and resulting in a random distribution of monomers inthe resulting polymer. In particular, in the batch process, thefunctional diol, emulsifier, polyol and any other OH-containingreactants react with the isocyanate simultaneously. Because theisocyanate can react with any OH group, and because the fluorinateddiol, emulsifier and polyol each have multiple OH groups, it isimpossible to determine with which OH group the isocyanate will reactand in which order. Consequently, the order of the monomers in theresulting polymer chain is impossible to predict.

In contrast, the fluorinated polyurethanes of the present invention areoften prepared by a split process in which each reactant has only onepossible reaction site. Specifically, in the first step of the process,the isocyanate can only react with the OH groups of thehydroxypolyalkylenoxy derivative of the perfluoropolyoxyalkane (1).Accordingly, the resulting chemical structure at each step of the splitprocess is controllable.

Moreover, the conventional batch process yields a very low amount of thedesired fluorinated pre-polymer. Because the batch process provides theisocyanate numerous reaction sites, the isocyanate will react morereadily with the emulsifier and any other OH-containing species ratherthan the hydrophobic fluorinated polyol. In contrast, thehydroxypolyalkylenoxy derivative of a perfluoropolyoxyalkane (1)includes hydrophilic end groups making the compound more friendly toreaction with isocyanate. In addition, the split process provides theisocyanate with only one reaction site option, thereby increasing thereactivity of the isocyanate with the fluorinated starting material.

To make a polyurethane coating composition for application to asubstrate, the water-dispersed, hydroxyl-terminated fluorinatedpolyurethane (7) is used as a base component, and a water-dispersibleisocyanate is used as an activator component. The base componentincluding the water-dispersed, hydroxyl-terminated fluorinatedpolyurethane (7) is reacted with the water-dispersible isocyanateactivator component. The water-dispersible isocyanate may be anysuitable aromatic, aliphatic or cycloaliphatic isocyanate. Any knownwater-dispersible isocyanates may be used as the water-dispersibleisocyanate activator component. Nonlimiting examples of suitablewater-dispersible isocyanates include trimer- and allophanate-basedpolyisocyanates manufactured from isophorone diisocyanate (IPDI) andhexamethylene diisocyanate (HDI), polyisocyanates prepared fromaminosulfonic acid modified chemistry, and blocked polyisocyanatesprepared from HDI or cyclohexylmethane diisocyanate (H₁₂MDI).

Nonlimiting examples of suitable trimer- and allophanate-baseddiisocyanates include Bayhydur 302, Bayhydur 303, Bayhydur 304 (formerlyBayhydur VP LS 2319), Bayhydur 305 (formerly Bayhydur VP LS 2336),Bayhydur 401-70 (formerly Bayhydur VP LS 2150/1), Bayhydur VP LS 2150BA,Bayhydur 3100 and Bayhydur XP-7165, all available from BayerCorporation. The properties of each of these exemplary water-dispersibleisocyanates are reported in Table 1 below. In Table 1, “% NCO” refers toisocyanate concentration, “Equiv weight” refers to equivalent weight,“NCO funct” refers to isocyanate functionality, “HM” meanshydrophilically modified, and “AMT” means allophanate modified trimer.

TABLE 1 Equiv Viscosity NCO Solids Type of % NCO Weight (mPa · s) functContent Isocyanate Bayhydur 302 17.3 ± 0.5 242.70 2300 ± 700  3.399.80%   HM HDI trimer Bayhydur 303 19.3 ± 0.5 271.60 2400 ± 800  3.4100% HM HDI trimer Bayhydur 304 18.0 ± 0.5 233.30 4500 ± 1500 3.8 100%HM HDI AMT Bayhydur 305 16.2 ± 0.5 259.20 6800 ± 600  3.8 100% HM IPDIAMT Bayhydur 401-  9.4 ± 0.5 446.80 600 ± 200 3.0 70% ± 2 HM IPDI trimer70 Bayhydur VP  9.4 ± 0.5 446.80 500 ± 200 3.0 70% ± 2 HM IPDI trimer LS2150BA Bayhydur 3100 17.4 ± 0.5 241.40 3300 ± 600  3.2 100% HDI standardBayhydur XP- 18.4 ± 0.5 228.30 1100 ± 200  3.0 100% HM HDI trimer 7165

Nonlimiting examples of suitable polyisocyanates prepared fromaminosulfonic acid modified chemistry include Bayhydur XP 2547, Bayhydur2487/1, and Bayhydur 2655, all available from Bayer Corporation. Theproperties of each of these exemplary water-dispersible isocyanates arereported in Table 2 below. In Table 2, “% NCO” refers to isocyanateconcentration, “Equiv weight” refers to equivalent weight, and “NCOfunct” refers to isocyanate functionality.

TABLE 2 Equiv Viscosity NCO Solids % NCO Weight (mPa · s) Funct ContentBayhydur XP 2547 23.0 ± 0.5 182.60 600 ± 200 3.0 100% Bayhydur 2487/120.5 ± 0.5 204.90 6000 ± 600  3.4 100% Bayhydur 2655 21.2 ± 0.5 198.103500 ± 1000 3.2 100%

Nonlimiting examples of suitable blocked polyisocyanates prepared fromhexamethylene diisocyanate (HDI) or cyclohexylmethane diisocyanate(H₁₂MDI) include Bayhydur VP LS 2240 and Bayhydur VP LS 2310, bothavailable from Bayer Corporation. The properties of each of theseexemplary water-dispersible isocyanates are reported in Table 3 below.In Table 3, “% NCO” refers to isocyanate concentration, “Equiv weight”refers to equivalent weight, and “NCO funct” refers to isocyanatefunctionality.

TABLE 3 Equiv Viscosity Type of Solids % NCO Weight (mPa · s) isocyanatecontent Bayhydur 2.5 1680 20 seconds* H₁₂MDI 35.0% ± 2.0 VP LS 2240Bayhydur N/A N/A 3000-10,000 HDI    37.5 ± 1.0 VP LS 2310 *Due to thelow viscosity, the value can only be reported in seconds.

The coating composition may further include conventional additives forcoating compositions, such as pigments, fillers, UV absorbers, flowaids, and rheology control agents. The coating composition may alsoinclude a catalyst. Although conventional coating compositions preparedusing the batch process and including catalysts have very short shelflives of only about three to six months, the use of catalysts in theinventive split process does not have an adverse effect on shelf life.The coating compositions of the present invention, prepared by theinventive split process and using catalysts have much longer shelflives, typically about one to two years.

The term “pigment” includes fillers and extenders as well asconventional pigments. Pigments are particulate materials which impartcolor or opacity to the final coating composition. Extenders and fillersare usually inorganic materials which can be used to reduce the cost ofa formulation or to modify its properties. Nonlimiting examples ofsuitable pigments include carbon black, titanium dioxide, magnesiumsulfate, calcium carbonate, ferric oxide, aluminum silicate, bariumsulfate, and color pigments. When used, the pigments can be present inan amount ranging from about 10 to 50 weight percent based on the totalsolids weight of the coating composition. For example, the pigments andfillers may be present in an amount ranging from about 20 to 40 weightpercent based on the total solids weight of the coating composition.

The polyurethane coating composition is, in certain embodiments, a“two-component system,” i.e., the water-dispersed, hydroxyl-terminatedfluorinated polyurethane base component including any additives andpigments is stored separately from the water-dispersible isocyanateactivator component. The individual components are maintained separatelyuntil shortly prior to application, when the two components are mixed,allowed to react, and then applied to the intended substrate.Cross-linking takes place after application on the substrate, and afterevaporation of any solvent and water in the composition.

The coating compositions of the present invention can be applied usingany suitable coating method, such as by brushing, spraying, dipping,rolling, flowing, and the like. Also, the coating compositions can beapplied to any suitable dry film thickness. For example, in certainembodiments, the coating composition is applied to a dry film thicknessranging from about 1 mm to 6 mm. In one embodiment, the coatingcomposition is applied to a dry film thickness ranging from about 2 mmto 4 mm.

The coating compositions of the present invention may be applied on aprimer and may be used as a topcoat, basecoat or clearcoat.Alternatively, the coating compositions may be used as a one-coatsystem, eliminating the need for a separate topcoat, basecoat and/orclearcoat.

The present invention has been described with reference to exemplaryembodiments and aspects, but is not limited thereto. Persons skilled inthe art will appreciate that other modifications and applications can bemade without meaningfully departing from the invention. For example,although the coating compositions are described as being useful foraerospace applications, they may be useful for other applications aswell. Also, while certain exemplary polyols and isocyanates are listedas suitable for the particular reactions, other suitable polyols andisocyanates may also be used. Accordingly, the foregoing descriptionshould not be read as limited to the precise embodiments and aspectsdescribed, but should be read consistent with and as support for thefollowing claims, which are to have their fullest and fairest scope.

1. A method of preparing a fluorinated polyurethane, comprising: (a)reacting a hydroxypolyalkylenoxy derivative of a perfluoropolyoxyalkanewith a first isocyanate to produce an isocyanate-terminated compound;(b) reacting the isocyanate-terminated compound with an emulsifier toproduce an acid- and hydroxyl-functional compound; (c) reacting theacid- and hydroxyl-functional compound with a second isocyanate to forman acid-functional, isocyanate-terminated compound; (d) reacting theacid-functional, isocyanate-terminated compound with at least one polyolto produce an acid- and hydroxyl-functional compound of higher molecularweight than the acid- and hydroxyl-functional compound produced in (b);and (e) neutralizing acid functional groups of the high molecularweight, acid- and hydroxyl-functional compound to form a fluorinatedpolyurethane.
 2. The method according to claim 1, wherein thehydroxypolyalkylenoxy derivative of a perfluoropolyoxyalkane isrepresented by formula (1):HO(CH₂CH₂O)_(n)CH₂—X—CH₂(OCH₂CH₂)_(n)OH  (1) wherein X is represented byformula (1A)—CF₂O(CF₂CF₂O)_(p)(CF₂O)_(q)CF₂—  (1A) wherein n is a rational numberranging from 1 to 10, and p and q are rational numbers satisfying10≦(p+q)≦180 and 0.5≦(p/q)≦2.
 3. The method according to claim 1,wherein the isocyanate-terminated compound is represented by formula(2):OCN—R—(CH₂CH₂O)_(n)CH₂—X—CH₂(OCH₂CH₂)_(n)—R—NCO  (2) wherein X isrepresented by formula (1A)—CF₂O(CF₂CF₂O)_(p)(CF₂O)_(q)CF₂—  (1A) wherein n is a rational numberranging from 1 to 10, p and q are rational numbers satisfying10≦(p+q)≦180 and 0.5≦(p/q)≦2, and R is selected from the groupconsisting of aliphatic groups, cycloaliphatic groups, aromatic groups,and mixtures thereof.
 4. The method according to claim 1, wherein theacid- and hydroxyl-functional compound is represented by formula (4):

wherein X is represented by formula (1A)—CF₂O(CF₂CF₂O)_(p)(CF₂O)_(q)CF₂—  (1A) wherein n is a rational numberranging from 1 to 10, p and q are rational numbers satisfying10≦(p+q)≦180 and 0.5≦(p/q)≦2, R₁ is an alkyl group, and R is selectedfrom the group consisting of aliphatic groups, cycloaliphatic groups,aromatic groups, and mixtures thereof.
 5. The method according to claim1, wherein the acid-functional, isocyanate-terminated compound isrepresented by formula (5):

wherein X is represented by formula (1A)—CF₂O(CF₂CF₂O)_(p)(CF₂O)_(q)CF₂—  (1A) wherein n is a rational numberranging from 1 to 10, and p and q are rational numbers satisfying10≦(p+q)≦180 and 0.5≦(p/q)≦2, and wherein: R and R₂ are independentlyselected from the group consisting of aliphatic groups, cycloaliphaticgroups, aromatic groups, and mixtures thereof, and R₁ is an alkyl group.6. The method according to claim 1, wherein the acid- andhydroxyl-functional compound produced in (d) is represented by formula(6):

wherein X is represented by formula (1A)—CF₂O(CF₂CF₂O)_(p)(CF₂O)_(q)CF₂—  (1A) wherein n is a rational numberranging from 1 to 10, and p and q are rational numbers satisfying10≦(p+q)≦180 and 0.5≦(p/q)≦2; and wherein: R and R₂ are independentlyselected from the group consisting of aliphatic groups, cycloaliphaticgroups, aromatic groups, and mixtures thereof, R₁ is an alkyl group, andR₃ is selected from the group consisting of polyether groups, polyestergroups, polyurethane groups and acrylic groups.
 7. The method accordingto claim 1, wherein the fluorinated polyurethane is represented byformula 7:

wherein X is represented by formula (1A)—CF₂O(CF₂CF₂O)_(p)(CF₂O)_(q)CF₂—  (1A) wherein n is a rational numberranging from 1 to 10, and p and q are rational numbers satisfying10≦(p+q)≦180 and 0.5≦(p/q)≦2; and wherein: R and R₂ are independentlyselected from the group consisting of aliphatic groups, cycloaliphaticgroups, aromatic groups, and mixtures thereof, R₁ is an alkyl group, R₃is selected from the group consisting of polyether groups, polyestergroups, polyurethane groups and acrylic groups, and

is a quaternary ammonium ion.
 8. The method of claim 1, furthercomprising dispersing the fluorinated polyurethane in water.
 9. A methodof preparing a fluorinated polyurethane, comprising: (a) reacting acompound represented by formula (1) with a first isocyanate to form acompound represented by formula (2)HO(H₂CH₂CO)_(n)H₂C—X—CH₂(OCH₂CH₂)_(n)OH  (1) wherein n is a rationalnumber ranging from 1 to 10, and X is represented by formula (1A)—CF₂O(CF₂CF₂O)_(p)(CF₂O)_(q)CF₂—  (1A) wherein p and q are rationalnumbers satisfying 10≦(p+q)≦180 and 0.5≦(p/q)≦2;OCN—R—(H₂CH₂CO)_(n)H₂C—X—CH₂(OCH₂CH₂)_(n)—R—NCO  (2) wherein R isselected from the group consisting of aliphatic groups, cycloaliphaticgroups, aromatic groups, and mixtures thereof; (b) reacting the compoundrepresented by formula (2) with an emulsifier to form a compoundrepresented by formula (4)

wherein R₁ is an alkyl group; (c) reacting the compound represented byformula (4) with a second isocyanate to form a compound represented byformula (5)

wherein R₂ is selected from the group consisting of aliphatic groups,cycloaliphatic groups, aromatic groups, and mixtures thereof; (d)reacting the compound represented by formula (5) with at least onepolyol to form a compound represented by formula (6)

wherein R₃ is selected from the group consisting of polyether groups,polyester groups, polyurethane groups and acrylic groups; and (e)neutralizing the compound represented by formula (6) with a tertiaryamine to form a fluorinated polyurethane represented by formula (7),wherein the tertiary amine is represented by NR′₃

wherein

is a quaternary ammonium ion.
 10. The method according to claim 9,wherein the first and second isocyanates are independently selected fromthe group consisting of isophorone diisocyanate, cycloaliphaticdiisocyanates, hexamethylene diisocyanate, tetramethylxylyenediisocyanate, and combinations thereof.
 11. The method according toclaim 9, wherein the emulsifier is represented by formula (3A):


12. The method according to claim 11, wherein the emulsifier is selectedfrom the group consisting of dimethylolbutyric acid anddiethylolpropionic acid.
 13. A fluorinated polyurethane comprising acompound represented by formula (7):

wherein: n is a rational number ranging from 1 to 10, each of R and R₂is independently selected from the group consisting of aliphatic groups,cycloaliphatic groups, aromatic groups, and mixtures thereof, R₁ is analkyl group, R₃ is selected from the group consisting of polyethergroups, polyester groups, polyurethane groups, and acrylic groups,

is a quaternary ammonium ion, and X is represented by formula (1A)—CF₂O(CF₂CF₂O)_(p)(CF₂O)_(q)CF₂—  (1A) wherein p and q are rationalnumbers satisfying 10≦(p+q)≦180 and 0.5≦(p/q)≦2.
 14. The fluorinatedpolyurethane according to claim 13, wherein the compound represented byformula (7) is dispersed in water.
 15. A polyurethane coatingcomposition comprising: a base component comprising the fluorinatedpolyurethane according to claim 14; and an activator componentcomprising at least one water-dispersible isocyanate.
 16. Thepolyurethane coating composition according to claim 15, wherein thewater-dispersible isocyanate is selected from the group consisting oftrimer- and allophanate-based polyisocyanates manufactured fromisophorone diisocyanate (IPDI), trimer- and allophanate-basedpolyisocyanates manufactured from hexamethylene diisocyanate (HDI),polyisocyanates prepared from aminosulfonic acid modified chemistry,blocked polyisocyanates prepared from HDI, and blocked polyisocyanatesprepared from cyclohexylmethane diisocyanate (H₁₂MDI).
 17. Apolyurethane coating composition comprising: a base component comprisinga compound represented by formula (7) dispersed in water

wherein: n is a rational number ranging from 1 to 10, each of R and R₂is independently selected from the group consisting of aliphatic groups,cycloaliphatic groups, aromatic groups, and mixtures thereof, R₁ is analkyl group, R₃ is selected from the group consisting of polyethergroups, polyester groups, polyurethane groups, and acrylic groups,

is a quaternary ammonium ion, and X is represented by Formula 1A—CF₂O(CF₂CF₂O)_(p)(CF₂O)_(q)CF₂—  (1A) wherein p and q are rationalnumbers satisfying 10≦(p+q)≦180 and 0.5≦(p/q)≦2; and an activatorcomponent comprising at least one water-dispersible isocyanate.
 18. Thepolyurethane coating composition according to claim 17, wherein thewater-dispersible isocyanate is selected from the group consisting oftrimer- and allophanate-based polyisocyanates manufactured fromisophorone diisocyanate (IPDI), trimer- and allophanate-basedpolyisocyanates manufactured from hexamethylene diisocyanate (HDI),polyisocyanates prepared from aminosulfonic acid modified chemistry,blocked polyisocyanates prepared from HDI, and blocked polyisocyanatesprepared from cyclohexylmethane diisocyanate (H₁₂MDI).